CN101988202B - 羧甲基壳寡糖希夫碱有机物碳钢海水缓蚀剂及其应用 - Google Patents

羧甲基壳寡糖希夫碱有机物碳钢海水缓蚀剂及其应用 Download PDF

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CN101988202B
CN101988202B CN200910017838.0A CN200910017838A CN101988202B CN 101988202 B CN101988202 B CN 101988202B CN 200910017838 A CN200910017838 A CN 200910017838A CN 101988202 B CN101988202 B CN 101988202B
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corrosion inhibitor
carboxymethyl chitosan
chitosan oligosaccharide
carbon steel
schiff base
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CN101988202A (zh
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李伟华
李云菊
张胜涛
曹琨
侯保荣
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14Nitrogen-containing compounds
    • C23F11/146Nitrogen-containing compounds containing a multiple nitrogen-to-carbon bond
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173Macromolecular compounds

Abstract

本发明涉及钢材(碳钢)海水缓蚀剂,具体地说是一种羧甲基壳寡糖芳草醛希夫碱类缓蚀剂及其应用,缓蚀剂成分是具有较好水溶性的羧甲基壳寡糖芳草醛希夫碱或其与磷酸氢二钠的一种或两种的组合。本发明缓蚀剂能有效防止海水对碳钢的腐蚀,具有用量低、缓蚀效率高、持续作用能力强的突出优点。本发明产品是一种“环境友好”的绿色缓蚀剂,来源广泛,具有广阔的市场前景和很好的应用价值。

Description

羧甲基壳寡糖希夫碱有机物碳钢海水缓蚀剂及其应用
技术领域
本发明涉及钢材海水缓蚀剂,具体地说是用以防止碳钢及其制品在苛刻的海水环境中碳钢材料的腐蚀和缓蚀剂过度消耗的一种羧甲基壳寡糖希夫碱缓蚀剂及其应用。
背景技术
海水是一种很有利用价值的自然资源,但是天然海水在所有利用领域必然会涉及碳钢等金属设备的防腐问题。在海水环境中保护金属设备的方法有多种,添加缓蚀剂是一种工艺简便、成本低廉、适用性强的措施。
近年来,对有机型缓蚀剂作用机理的研究表明:有机分子中如果含电负性较大的O、N、S、P等原子、不饱和键或者大共轭体系,一般来说都具有较好的缓蚀效果,因此有机缓蚀剂发展很快,应用广泛,但是使用这些缓蚀剂也会产生缺点,如可能污染产品,可能对生产流程产生不利影响等,因此开发研制绿色环保型有机缓蚀剂成为近年来研究的热点。
壳寡糖也叫壳聚寡糖,是将壳聚糖经特殊的生物酶技术处理而得到的一种全新的产品,是水溶性较好、功能作用大、环保无污染的低分子量产品。它具有壳聚糖所没有的较高溶解度,具有独特的生理活性和功能。席夫碱是一类非常重要的含氮化合物,因它的基本结构中含>C=N-结构,其杂化轨道上的N原子具有孤对电子,N原子依靠其孤对电子与铁表面的d轨道形成稳定的配位键,提高铁在腐蚀介质中的阳极活化能,从而降低铁的腐蚀速率,所以在腐蚀与防护方面赋予它重要的化学意义
羧甲基壳寡糖芳草醛希夫碱(CM-CSB)是经化学改性后的壳寡糖衍生物,它具有良好的水溶性,其分子中含一NH、一OH、一COOH、-CH=NH等吸附基团,能有效配位金属离子,使有机分子吸附在金属表面,形成保护膜,从而抑制金属腐蚀。因此,对羧甲基壳寡糖希夫碱类缓蚀剂的研发具有较高的生产价值和广阔的市场前景。
发明内容
本发明的目的在于提供一种高效、环保的羧甲基壳寡糖希夫碱类绿色海水缓蚀剂及其应用。
为实现上述目的,本发明采用的技术方案为:
一种羧甲基壳寡糖芳草醛希夫碱有机物碳钢海水缓蚀剂,所述缓蚀剂的有效成分是羧甲基壳寡糖芳草醛希夫碱或磷酸氢二钠的一种或两种的组合;组合比例可为任意比。二者按重量份数的复配较好为:(100-800)∶(1000-2000)。
所述缓蚀剂为羧甲基壳寡糖芳草醛希夫碱时,羧甲基壳寡糖芳草醛希夫碱的缓蚀效果有赖于缓蚀剂的浓度,其质量浓度为(100-800)mg/L,在海水介质中,当缓蚀剂浓度达到800mg/L时对A3碳钢的缓蚀作用达到最大。
所述缓蚀剂为磷酸氢二钠时,在海水介质中,磷酸氢二钠质量浓度为1000-2000mg/L;
所述缓蚀剂为羧甲基壳寡糖芳草醛希夫碱和磷酸氢二钠的组合时,二者于海水介质中的浓度为:100-800mg/L和1000-2000mg/L。
本发明的原理在于:本发明涉及的羧甲基壳寡糖芳草醛希夫碱(CM-CSB)是经化学改性后的壳寡糖衍生物,它具有良好的水溶性,其分子中含一NH、一OH、一COOH、-CH=NH等吸附基团,能有效配位金属离子,使有机分子吸附在金属表面,形成保护膜,从而抑制金属腐蚀。
本发明的有益效果是:、
1.成本低。本发明缓蚀剂为羧甲基壳寡糖希夫碱类,合成步骤简单,原料廉价易得;属绿色型缓蚀剂;
2.环境友好。本发明缓蚀剂为羧甲基壳寡糖希夫碱类化合物,为有机缓蚀剂,与目前常用的无机缓蚀剂相比,无毒无害,不存在使用后的环境问题;对环境和生物无毒无害,符合绿色缓蚀剂发展的趋势;
3.用量低,使用效果好。本发明用于碳钢海水缓蚀,添加少量的缓蚀剂就可有效抑制金属材料在海水环境中金属的过度浸蚀(即有害腐蚀)以及缓蚀剂的过度消耗,与目前常用的缓蚀剂比较,具有用量低、缓蚀效率高、持续作用能力强的突出优点。
4.持续能力强。本发明能承受清洗条件的变化,如清洗剂浓度、流速等,不影响缓蚀剂的缓蚀效果。
具体实施方式
羧甲基壳寡糖芳草醛希夫碱的结构及及制备方法如下:
结构:
Figure G2009100178380D00021
制备方法:
Figure G2009100178380D00031
本发明按照GB10124-88《金属材料实验室均匀腐蚀全浸试验方法》进行失重试验。
实施例1
介质为3.5%NaCl溶液,介质用量500ml,加入400mg羧甲基壳寡糖芳草醛希夫碱(浓度为800mg/L),在室温条件下将待碳钢浸没在该介质中15d。
通过试验测试获得的最高缓蚀效率为82.54%,对于有机物而言显示为高效的缓蚀剂。
按上述操作过程,分别测定羧甲基化壳寡糖芳草醛希夫碱不同浓度的缓蚀效率如下:
Figure G2009100178380D00041
实施例2
介质为海水,介质用量500ml,加入400mg羧甲基壳寡糖芳草醛希夫碱,在室温条件下将待碳钢浸没在该介质中15d。在室温条件下将碳钢钢浸没在该介质中浸没15d。
通过试验测试获得的最高缓蚀效率为81.90%,对于有机物而言显示为高效的缓蚀剂。
实施例3
介质为3.5%NaCl溶液,介质用量500ml,加入1000mg磷酸氢二钠,在室温条件下将待碳钢浸没在该介质中15d。
通过试验测试获得的最高缓蚀效率为90.09%,对无机缓蚀剂而言显示为高效的缓蚀剂。
实施例4
介质为天然海水溶液,介质用量500ml,加入1000mg磷酸氢二钠,在室温条件下将待碳钢浸没在该介质中15d。
通过试验测试获得的最高缓蚀效率为89.29%,显示为高效的缓蚀剂。
实施例5
介质为3.5%NaCl溶液,介质用量500ml,加入400mg羧甲基壳寡糖芳草醛希夫碱和500mg磷酸氢二钠,在室温条件下将待碳钢浸没在该介质中15d。
通过试验测试获得的最高缓蚀效率为92.49%,显示为高效的缓蚀剂。
实施例6
介质为天然海水溶液,介质用量500ml,加入400mg羧甲基壳寡糖芳草醛希夫碱和500mg磷酸氢二钠,在室温条件下将待碳钢浸没在该介质中15d。
通过试验测试获得的最高缓蚀效率为90.12%,显示为高效的缓蚀剂。
本发明缓蚀剂能有效防止在苛刻的海洋环境过程中对碳钢的腐蚀,具有用量低、缓蚀效率高、持续能力强的突出优点。本发明产品是一种“环境友好”的绿色缓蚀剂,来源广泛,具有广阔的市场前景和应用价值。

Claims (2)

1.一种羧甲基壳寡糖芳草醛希夫碱有机物碳钢海水缓蚀剂,其特征在于:所述缓蚀剂为羧甲基壳寡糖香草醛希夫碱和磷酸氢二钠的组合,二者按重量份数的复配为:(100-800)∶(1000-2000)。
2.一种权利要求1所述碳钢海水缓蚀剂的应用,其特征在于:所述缓蚀剂为羧甲基壳寡糖香草醛希夫碱和磷酸氢二钠的组合,二者于海水介质中的浓度为:100-800mg/L和1000-2000mg/L。
CN200910017838.0A 2009-08-07 2009-08-07 羧甲基壳寡糖希夫碱有机物碳钢海水缓蚀剂及其应用 Expired - Fee Related CN101988202B (zh)

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CN102433564B (zh) * 2011-09-23 2013-09-18 桂林理工大学 邻氧乙酸苯甲醛缩取代苯胺希夫碱缓蚀剂的制备方法
CN103497122B (zh) * 2013-09-27 2015-07-22 桂林理工大学 3,5-二溴水杨醛缩对氨基苯甲酸席夫碱基聚乙二醇月桂酸单酯及其应用
CN103484091B (zh) * 2013-09-27 2015-12-23 桂林理工大学 邻香草醛缩对氨基苯甲酸席夫碱基聚乙二醇月桂酸单酯及其应用
CN104498958B (zh) * 2014-12-09 2017-06-16 刘旸 一种海上油田采出油管道中使用的硫化氢缓蚀剂的制备方法
CN111748048B (zh) * 2020-08-03 2020-12-11 西南石油大学 一种改性壳聚糖酸化缓蚀剂的制备方法
CN115125540A (zh) * 2022-06-13 2022-09-30 大连理工常熟研究院有限公司 一种基于5-羟甲基糠醛修饰壳聚糖的碳钢酸洗缓蚀剂
CN116023524A (zh) * 2023-02-04 2023-04-28 西南石油大学 一种壳寡糖衍生物缓蚀剂及其制备方法
CN117164128B (zh) * 2023-11-03 2024-01-02 烟台康恩环保科技有限公司 一种高溶解氧水质用有机阻垢缓蚀剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1687142A (zh) * 2005-03-30 2005-10-26 中国科学院海洋研究所 羧甲基壳聚糖希夫碱衍生物及其制备方法
CN1727363A (zh) * 2005-07-25 2006-02-01 中国科学院海洋研究所 N-取代羧甲基壳聚糖及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1687142A (zh) * 2005-03-30 2005-10-26 中国科学院海洋研究所 羧甲基壳聚糖希夫碱衍生物及其制备方法
CN1727363A (zh) * 2005-07-25 2006-02-01 中国科学院海洋研究所 N-取代羧甲基壳聚糖及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
霍晋涛.聚氧乙烯-聚乳酸温敏型药物传递体系的制备与性能研究.《武汉理工大学硕士学位论文》.2008,第43页. *
高忠良等.低分子量的羧甲基壳聚糖的制备.《食品科技》.2003,(第9期),60-62. *

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